Polymerization of resins



Patented Feb. 5, 1935 v p 7 $990,215 7 g POLYMERIZATION F RESINS I George Kenneth Anderson, Pittsburgh, Pa., as-

signor to The Neville Company, a corporation,

of Pennsylvania mutating. Application July 5, 1933,

Serial No. 679,085 6 clai s. (01. gee-g7) This invention relates to the polymerization of coumarone type resin. It is important-for certain'purposes'that coumarone resin have a high degree'of solubility T: in the solvents of commercial grade, such as coal tar naphtha, petroleum distillates, and hydro-' genated' petroleumsolvents, employed as solvents for the resin in the manufacture of paint and varnishbasesfi The problem is to so conduct a 1 polymerization process for production of the resin that anotherwise high grade'of 'resin'having a high degree of solubility isproduced." one meth- 0d of improving-the solubilityxof coumaroneresin over that obtained by standardmethodsofbulk' polymerization is" disclosed"and"claimed in my? I copending app1ication,'-Seria1 No. 592,854, filed- February 13', l932'a-now Patent 1,922,342. present invention constitutes an improvement in the'lcontrol of the polymerizing reaction, with a consequentimprovement in' 'certain qualities of the resin producedp 3 i 4 While his unnecessary to detail the steps by which I' arrived :at' my'conclusion, I have discovered that if the catalyst, preferably sulphuric acid, be in-a state'of finei'dispersionin a diluent, the actual reactiontime' may be "controlled',and a control of the solubility 'of'theresin'may-be' obtained.-- The Lfine dispersionvof catalystin a prepared bath creates conditionsigenerally favor able :to'the control of a polymerizing reaction of thisnature, and of itself tends to modify the polymerizing reaction resulting from running sulphuricacidinto a batch containing the poly'- me'r'izable bodies, I The fact, namely, that'the' particularly fine dispersion of the catalyst'leads' to animprovement in the qualities of the resin produced, I'have established by a succession of tests. The corollary control of reaction time can be effected, so far as I am aware, only .by the fine andintimate dispersion of the catalyst. 'It should be understood that reaction time I'may roughly define as the total period during which polymerizable but unpolymerized bodies are brought'into contact with the catalyst.

It is, of course, true, andis expressed in the prior 'art',.tthat a lengthened. reaction time, accompanied, by 'some retardation in the rate of addition in the formation of polymers, may be obtained by running a'dilute catalyst slowly into a lean starting material, that is, astartingmaterial containingi'arelatively small percentage of polymerizable bodies. Such. practice is, however, ineflicient, in that the resulting resin production is small'for'the size of batch'employed. While 5 such procedure as thatnoted mayito some degree tiontime will extend the reaction time, and to some extent decrease the rateof polymerization, it doesnot.

give a control of reactiontime, and does not" uniformly'decreaseor make controllable the rate of" addition in the polymerizing action.

In my above-noted pending application, 'successive relatively small charges of catalyst and material containing the polymerizable bodies areadded successively to a relatively large 'body of: diluent, until a resincont'ent of substantial quarrel tityhasbeen built up in the blend. This method lOl;

may be considered successful in producing a cou-i I have found that the-fine dispersion of acid througha body of diluent, and. the contact "of material containing the polymerizable bodies with the mixture containing the? acid in a fine'state'of, dispersion, also provides a reactionin which ai relatively Small quantity p ymerizablebodies are exposed to the action: of the catalyst-iatqany,

one time and additionally permits a relatively ac curate control of slichqua'ntity of polymerizable: bodies throughout-thetime*of-reaction.

I It may be'ini tiallyunderstood that if polymeriz'able bodies be supplied toan activated bathcon taining a fine dispersion of'catalyst inan inertliquid at a slow rate of supply, thereaction' time may-be made to coincide approximately to the period of supply of thepolymerizable' bodies." 'If the rate of supplybe relatiyelyrapidpthe reac be" somewhatlonger thantheperiod ofsup'ply." 'As a general example v cedure, I first 'effectthe:dispersion of 'aliquid catalyst, preferably sulphuric acid, in a body of diluent, by violently agitating the acid-therein;

uid containing polymerizable bodies I as well as of my polymerizing prothevolu'me of diluentfa volume of 66 sulphuric acid equal to from about1% of the total volu in'e of resin forming liquid and diluent to 5% of such" as much as 5% of 66 sulphuric acid withr'espectl to the total volumeof other liquids. 7 As a diluent I know that a hydrocarbon distillate, such as petroleum distillate or refined naphtha, may be used. These distillate's' arein v ert under the conditions of the processgand serve to some'extent as selective solvents for' the'resinous polymers which are formed. .I Qfpthe obtained from the distillation of coal, which con; k

' 1.10%.. thecombined volume of crude solvent is added gradually-desirably two classes, I prefer the petroleum distillates as lending themselves more readily to reaction control, being more selective as solvents of the resinous polymers, and as facilitating the steps of resin recovery subsequent to polymerization.

After the acid has been thoroughly dispersed through the body of diluent, and not before thorough dispersion, I begin the addition of the liquid which contains the polymerizable bodies. Thisliquid is desirably a crude solvent naphtha containing a determined percentage of polymerforming bodies, but may be sonic .otl'ifliquid tains equivalent bodies. V I

The liquid containing the polymerizable bodies in a running stream-and its rate of supplyis controlled throughout the period of its supply. The of supply of the liquid containing the polymer-- izablebodies is varied roughly in accordance with the desired characteristics of the resin to be produced, taking into consideration the concen trationof the polymer-forming bodies in the liquid, together with the volume ratiofof this polymer-producing liquid, orstartin liquid, to

the diluent. i

I I have taken, for example, 900 gallons of starting material containing 53% oflpolymerizable bodies, and made 'theratio of this liquid'to dil-fl I. went 1:3. Using sulphuricv acid for .polym'eriza, 'tion, in this instance about 1.7% 66". acid; the

period of supplyof the starting liquid to the:

prepared, activated, bath was approximately six minutesgand the bath was prec'ooledlto 18C.

The resulting resin possessed a melting .point, of 126 .C. and a precipitation temperatureiof 16C. from 'Stoddard solvent naphtha. '5 It. may be noted-that in this example the "reaction time was butslightly longer than the period ,of supply,

- ab0l1't.90%"0f the temperature rise having' taken placeduring thesix-minute. period of supply." *The foregoing mayibeconsidered as typiiying a;highly-useful aspectof the invention, giving a melting point adequately vhigh for-most purposes;

with very good solubility a iyield adequately high'forcommercial practicer Returning j to the general I conditions loft process, temperature control'seemsto be with my method of less importance than is ;the case 1 with a method in which acid is run into a batch containing polymerizable. bodies. It. is important,

' however, :that the activated bath be precooled,

or thatheat abstracting conditions be maintained throughout the periodlof reaction. It is desirable that there be agitation to mechanically-disk perse the added liquid containing the-polymerizable bodies through the activated bath.- It is a factthat the crude solvent naphtha will-tend to'disperse. of its own accord through the body offlthejbfith; and, theacid being-finely dispersed, the tendencyif'or intense localactioni to occuris lessened. I1, however, reaction tlmebe made 1 relatively "short; agitation becomes of increased.

mportance. V I I v e Following t po ymerizing reactiomtheliquid I is decanted from the precipitate. and washed'free of the polymerizing agent and remaining impurities. -It is distilled. The resinous material is itself a valuable product tained by. using a starting liquid, which is particularly lean or by operating in particularly high dilution. I have, however, discovered inpractice that controlling the reaction time by control of the rate of supply of the liquid containing polymerizable bodies, I am able to obtain a resin of r merizable bodies, and haveapportioned this in theratio of one volumeof this starting liquid ytothreevolumes of petroleum distillate. I used I as a catalyst 66 sulphuric acid in a volume of naphtha and' petroleum distillate. The acid was dispersed thoroughly in the diluent, to provide iafnflactiyated'bath prior to the introduction of "the crude solvent naphtha. cooledto a'temperature of 16 C. The crude solvent naphtha was run into the bath with agi- The bath was prea melting point of approximately-154 (L -and" a precipitation, temperature from Stoddard 'sol-' vent naphthaof approximately-29 C. :The? surprising. feature illustrated by this exe ample is. thepossibillty of producing a couma-'?.

;- As an extreme examplelo'f' the productioniof low-melting-point resin, I have-taken crude sol vent naphtha of about 55% polymerizable' 'con-r tent, and by'extending the period of supply, and

cipitation fror'nrjStoddard solvent naphthaf at-.10 v

C. The initial bath temperature was C.,"and the volu'meof acid was 09% 66 sulphuric acid; An incident to, such extreme. example is that a relatively low yield of, solid resin is "obtained, and that there is an accompanying formation of a relatively great quantity-of heavy oil, which may be considered. as? the product i of one of :the initial, stagesflof polymerization; This -heavy :oil

It willibe readily understoodfrom the above that, wholly-aside from any theory of polymerization, my inventionlconsists primarily inthe use of a preformed bath offidiluent andcatalyst, with the catalyst finely and thoroughly dispersed, in the; bath, and, secondarily, in theadditionof liquid. containing polymerizable. bodies to this bath at a controlled rate ofsupply.

- "Itishould be understood that the formation ofan activated bath of inert'diluent and catalyst i is in itself, of primarymerit. By preparing such anactivatedbath, and running the liquid'con-f taining the 'polymerizable "bodies. into it "even rapidly,iI have been able toproduce vcoumarone resin having a solubility better than .would result under otherwise similar conditions, by. adding the acid to a batch of diluent and liquid contain-' ing the polymerizable bodies. In orderltoobtain the advantage of. the activated bath'under such circumstances, it is necessary that the'rate of supply of the liquid;containing"the p'olymerizable bodies'be sufiicieritly retarded; or gradual, and the agitation'be such? as to cause dispersion ofthis liquid through the bath containing thedispersed acid. That is, the rate of supply must'be sum-- ciently slow, and the agitation adequate to. prevent intense action in any region of the'bath.

' Intestingthe solubility of the resin by preclpl tation from Stoddard solvent naphtha, I make a 20% solution by weight of the resin in the solvent, and cool back to the temperature at which precipitation occurs.

I claim as my invention:

1. In the bulk production of coumarone resin by catalytic polymerization the herein described polymerization method which comprises preparing in advance an activated bath by thoroughly dispersing a catalyst in a body of liquid diluent which is inert to the polymerizing reaction and which is a solvent for the resultant resin but in which the catalyst is insoluble, establishing heat abstracting conditions for the activated bath, and gradually adding to and dispersing in said activated bath a charge of liquid containing bodies polymerizable into coumarone resin, the said liquid containing the resin-forming bodies being added at a rate adequately slow to produce intimate immediate distributed contact as the liquid is added between the insoluble catalyst and the resin-forming bodies.

2. A process in accordance with claim 1 in which the inert liquid diluent a solvent for the resultant resin is a refined'liquid hydrocarbon derived from the distillation of coal and the catalyst is sulphuric acid. I I,

3. A process in accordance with claim 1 in which the inert liquid diluent a solvent for the resultant resin is a petroleum distillate and the catalyst is sulphuric acid.

4. In the bulk production of coumarone resin by catalytic polymerization the herein described polymerization method which comprises preparing in advance an activated bath by thoroughly dispersing in a body of liquid diluent which is inert to the polymerizing reaction and which is a solvent for the resultant resin but in which sulphuric acid is insoluble, sulphuric acid as a catalyst for polymerization, said sulphuric acid being apportioned to the volume of inert liquid diluent to provide an active content of catalyst in the bath not substantially greater than that resulting from dispersion in the diluent of a vol ume of 66 Baum sulphuric acid equal to five per cent. the volume of inert liquid diluent, and.

adding to and dispersing in the bath liquid containing bodies polymerizable into coumarone resin.

5. A process in accordance with claim 4 in which the inert liquid diluent a solvent for the resultant resin is a refined liquid hydrocarbon derived from the distillation of coal.

6. A process in accordance with claim 4 in which the inert liquid diluent a solvent for the, resultant resin is a petroleum distillate.

GEORGE KENNETH ANDERSON. 

